Metallized mixed azo-dyestuffs



United States Patent 2,970,137 METALLIZED MIXED AZO-DYESTUFFS Herbert E.Whitlock, Clark, N.J.,assign0r to Verona- Pharma Chemical Corp.,Bayonne, N.J., a corporation of New Jersey No Drawing. Filed Sept. 9,1958, Ser. No. 759,857

2 Claims. (Cl. 260-145) The present invention is directed to newmetalliferous ale-dyestuffs, more particularlyto those which contain oneatom of chromium or cobalt bound in complex union with two molecules ofdifferent monoazodyestuffs.

Dyestulfs of this general character have been known and used for aconsiderable number of years. They are generally useful in the dyeing ofwool. While such. dyestuffs have been satisfactory to a certain extent,it has become evident that the properties could be improved.

It is, therefore, among the objects of the present invention to devisedyestufis of the character described which exhibit increased fastness tolight and improved fastness to washing.

In practicing the invention there are provided two different monoazodyestuifs, one of the dyestuffs being free from sulfonic acid groups, orsubstituted sulfonic acid groups such as sulfonarnides, and alkylsulfones, and free from carboxylic acid groups, other thanthose in orthoposition to the azo linkage,.which monoazo-dyestuli corresponds to. thegeneral formula:

"wherein R represents a naphthalene radical, which may it carry one ortwo chlorine groups, and, is attached to the am group in a positionvicinal tothe group 'C; A represents hydroxy or carboxy groups; B and Brepresent hydrogen, halogen, nitro or acetylamino groups; C representshydroxy, amino, alkylor arylamino groups; and D represents hydrogen,hydroxy or acylated amino groups, where the acyl group is the radical offormic, acetic, benzoic, rnethylca'rbonic or ethylcarbonic acids.

The other monoaZo-dyestuff is free frorncarboxylic acid groups otherthan those in the ortho-position to the azo linkage but carries one freesulfonic acid group atwherein R represents a naphthalene'radicaLwhichmay carry 1 or 2 chlorine groups, A represents hydroxyor carboxy groups;B represents hydrogen, halogen, nitro or acetylarnino groups; Crepresents hydroxy, amino,

alkylor arylamino groups; D represents hydrogen, hy? droxy or acylatedamino groups, where the acyl group 1 is the radical of formic, acetic,benzoi'c, methyl-carbonic or ethylcarbqnic acids; and one X representshydrogen and the other X is represented by the general formula:

, wherein Y represents hydrogen, methyl, ethyl, hydroxyethyl, cyclohexylor phenyl groups.

The essence of the invention is the linkage of the free4.6-dinitro-2-aminol-hydroxybenzene Patented Jan, 31, 19 61 4- or5-chloro-2-amino-l-hydroxybenzene 4- or 5- or6-nitro-2-arnino-l-hydroxybenzene 4.6-dichloro-2- amino-l-hydroxybenzene4-chlor0-5 or 6-nitro-2-amino-l-hydroxybenaene4-nitro-6-chloro-2-amino-l-hydroxybenzene4-nitro-6-acetylarnino-2-amino-l-hydroxybenzene6,-nitro-4-acetylamino-2-arriino-l-hydroxybenzene Z-aminobenzoic acid "Iin conjunction with the following representative coupling components: lr,

2-hydroxynaphthalene Z-aminonaphthalene 2-methylamino naphthaleneZ-ethylamino naphthalene Z-hydroxyethylamino naphthalene 2-phenylaminonaphthalene 8-acetylamino-2-hydroxynaphthalene5-acetylarnino-2-hydroxynaphthalene 8-formylamino-2-hydroxynaphthalene5-forinylamino-2-hydroxynaphthalene 8-benzoylamino-2-hydroxynaphthalene5-benzoylamino-Z-hydroxynaphthaln' 8-carbethoxyamino2-hydroxynaphthalene S-carbethoxyamino-2-hydroxynaphthalene 5.8diohloro-l-hydroxy naphthalene.

The monoazo-dyestuffs carryingthe free sulfonic'acid groups, which serveas the other starting materials for the present dyes can conveniently beprepared by coupling into the components set forth above under (b) withthe tached to an aliphatic chain, which monoazo-dyestuffi corresponds tothe general formula:

; 4-chloro 2 amino 1 hydroxybenzene-S-sulfonann,do-

following representative diazo components:

2-arnino-1-hydroxybenzene-4- or S-sulfonamido-N-omegaethane sulfonicacid Z-amino-l-hydroxybenzene-4- or 5-sulfonamido-N-methyl-N-omega-ethane sulfonic acid 2-amino-1-hydroxybenZene-4- or5-sulfonamido-N-ethyl- N-omega-ethane sulfonic acid 2 2-amino P '1hydroxybenzene-4- or S-sulfonamido- -hydroxyethyl-N-omeg'a-ethanesulfonic acid-. 2-amino-1-hydroxybenzene-4- or 5-sulfonamido-N-phenyl-N-omega ethane sulfonic acid N-omega ethane sulfonic acid :4-chloro 2amino 1 hydroxybenzene-S-sulfonamido- N-methyl-N-omega-ethane sulfonicacid 4-chloro 2 amino 1 hydroxybenzene-5-sulfonamido-N-ethyl-N-omega-ethane sulfonic acid ,4-chloro 2 amino 1hydroxybenzene-S-sulfonamido- N-hydroxyethyl-N-omega-ethane sulfonicacid 4-chloro 2 amino 1 hydroxybenzene-5-sulfonamido-N-phenyl-N-omega-ethane sulfonic acid 6-chloro 2 amino 1hydroxybenzene-4-sulfonamido- N-omega-ethane-sulfonic acid 7 t I6-chloro 2 amino 1 hydroxybenzene-4-sulfonamido- N-methyl-N-omega-ethanesulfonic acid 6-chloro 2 amino 1 hydroxybenzene-4-su1fonamido-N-ethyl-N-omega-ethane sulfonic acid 6-chl oro 2 amino 1hydroxybenzenei-sulfonamido!- 2 hydroxynaphthalene '6 6-chloro 2 amino 1hydroxybenzene-4-sulfonamido- N-phenyl-N-omega-ethane sulfonic acid4-nitro -.2 amino 3 1 hydroxybenzene 6 sulfonamido- N-omegaethane-sulfonic acid 4-nitro 2 amino 1 -hydroxybenze ne 6 sulfonamidoj,N-rnethyl-N-omega-ethane sulfonic acid 4-,nitro 2 amino l--hydroxybenzene .6-'sulfonamido- N-cthyl-N-omega-ethane sulfonic acid4-nitro -.52 amino -'1 hydroxybenzene 6 .sulfonamido-N-hydroxyethyl-N-omega-ethane sulfonic acid 4-nitro 2 amino :1}hydroxybenzene 6 sulfona'rnido- N-phenyl-N-omega-ethane sulfonic acid6-nitro 2 amino 1 hydroxybenzene 4 sulfonarnido- N-omega-ethane-sulfonicacid p v 6-nitro 2 amino 1-.hydroxybenzene 4 sulfonamido-N-methyl-N-omega-ethane sulfonic acid 6-nitro -.2 amino- 1hydroxybenzene 4 sulfonamido- N-ethyl-N-omega-ethane sulfonic acid6-nitro 2 amino 1 hydroxybenzene 4 sulfonamido-N-hydroxyethyl-N-omega-ethane sulfonic acid 6-nitro 2 aminolhydroxybenzene 4 sulfonamido- N-phenyl-N-omega-ethane sulfonic acid.

, .In addition the monoazo-dyestufifs carrying the free sulfonic acidcan conveniently be prepared by coupling diazo components set forthabove under (a) into the following representative coupling components:

2-amino naphthalene-S- or 6-sulfonarnido-N-ethyl-N-,

omega-ethane sulfonic acid Z-amino-naphthalene-S- oro-sulfonamido-N-hydroxyethyl-N-omega-ethane sulfonic acid 2-aminonaphthalene-S- or 6-sulfonamido-N-phenyl-N- omega-ethane sulfonic acidsulfonarnido N omegaethane sulfonic acid I 2 hydroxynaphthalene 6sulfonamido N -.rnethyl N- omega-ethane sulfonicacid -2hydroxynaphthalene 6 sulfonamido N ethyl N- omega-etha'ne sulfonic acid2 hydroxynaphthalene -6 -'sulfonamido N hydroxyethyl-N-omega-ethanesulfonic acid 2 hydroxynaphthalene 6 sulfonarnido 'N phenyl-N-omega-etha'ne sulfonic acid.

Theyarious components specifically.-namcd above are to be considered asrepresentative 'of'the many compounds of'the type described which aresuitable for the invention, and they do not limit the invention to thespecific compounds named. v

The complex metallif'e'rous dyestuffs of the present invention can bemade by treating a'mixture of substantially equimolecular quantities'of'th'e twoditferent mo'noazodyestutts, one of which corresponds toFormula 1 and the other to Formula 2, which dyestuffs "are preparedusing appropriate components'fr-om the lists shown, with an agentyielding metal in 'such a manner that the re- 'sulting metalliferousdyestuff contains one atom 'of metal bound in complex union with twomolecules of different monoazo-dyestuffs namely (1) and (2).

In carrying out this process it is generally of advantage totrea't amixture of one molecular proportion of each of the two differentdyestuffs with a quantity of an agent yielding metal corresponding toabout 1 atomic proportion of metal, and carrying out the metallizationin a weakly acid to strongly alkaline medium. Accordespecially chromiumcompounds of hydroxy carboxylic acids or dicarboxylic acids, whichcontain the metal in "*a' complex union, in addition the alkali salts ofchromic 4 acid, can be used in the presence of reducing agents.

The conversion of the dyestuffs into the'com'plex metal compounds isadvantageously carried out in a water medium at a raised temperatureunder atmospheric or superatmospheric pressure. The finished productsare isolated in the usual manner.

The new metal-containing dyestuffs are soluble in water and are suitablefor dyeing'and printing of a'variety of materials, primarily however forthe dyeing of materials such as wool andsilk but also for the dyeing andprinting of synthetic fibers such as superpolyamides andsuperpolyurethanes. They are especially suitablefor dyeing from weaklyalkaline, neutral or weakly acid bath. The wool dyeings thus obtainableare distinguished by good levelling capacity, by excellent lightfastness and unexpectedly high wash fastness.

The following examples illustrate the invention, the parts'being byweight unlessotherwise stated and 1 mol" denoting, as is usual, thenumberof grams corresponding the molecular weight, and the relationbetween parts by weight and parts by volume being the-same-as thatbetween thekilogram and the liter:

EXAMPLE 1 .1 mol of the dyestutf from diazot'ized4-nitro-2-aminol-hydroxy-benzene and 8-acetylamino-2-hydroxynaphtha-.lene are slurried with .1 mol of the .dyestufi from Idiazotized :2amino 1 hydroxybenzene 4 sulfonamido-N-methyl-N-omega-ethane sulfonicacid and Z-hydroxynaphthalene in water, the total volume being 4000volume .parts. This slurry is heated to C. and 'is brought into solutionwith sodium hydroxide. To this is added a solutionof 16.8 parts sodiumbichromate, 20.2 .parts dextrose in 200 parts water. The mixture is heldat 90 C. until the metallization is completed.

The metallized dyestuff .isisolated by the addition of sodium chloride,followed by filtration. When dry, the dyestufi is a water soluble darkpowder, which dyes wool from a neutral or weakly acid bath in deep blackshades of excellent fastness properties.

The monoazo-dyestufi tree of sulfonic acid groups is prepared asfollows:

15.4 parts 4-nitro-2-amino-l-hydroxybenzene are dissolved in parts waterand 29 parts of 30% hydrochloric acid. The solutionis cooled to 10 C.and is diazotized with 6.9 parts of sodium nitrite. Into .theformed'diazo suspension there is run a solution of 20.1 parts8-acetylamino-2-hydroxynaphthalene in 75 parts water and 17.5partssodium hydroxide. The coupling temperature is kept down with ice.When the coupling is completed the dyestuif is isolated by filtrationandis I analyzed.

The monoazo-dyestufl? carrying the sulfonic acid group is prepared asfollows:

31 parts Z-amino-1-hydroxybenzene-4-sulfonamide-N- methyl-N-omega-ethanesulfonic acid are suspended in. 100 parts water with 17.5 parts of 30%hydrochloric acid and are diazotized with 6.9 parts sodium nitrite at 5C. To the suspension of the 'diazo is added a solution of 15 parts betanaphthol in 100 parts water and .10 parts sodium hydroxide, thetemperature being kept down with ice. When the coupling is completed thedyestulf is-isolated with salt and is filtered. It is then analyzed.

The 2 amino l hydroxybenzene 4 sulfonamido- Namethyl-N-omega-ethanesulfonic acid can be conveniently prepared by condensing1-chloro-2-nitro-benzene-4-sulfonchloride in aqueous alkaline mediumwith methyltaurine (CH N'HCH CH SO H), hydrolyzing the formed 2 nitro lchlorbenzene 4 sulfonamido- N-methyl-N-omega-ethane sulfonic acid atelevated temperature with caustic to 2 nitro l hydroxybenzene 4sulfonamido N methyl N omega ethane sulfonic acid, and finally reducingthe so formed nitro compound with iron and acetic acid in an aqueousmetaurine or cyclohexyltaurine, when the following new amines areformed:

2 amino 1 hydroxybenzene 4 sulfonarnido 7 N- omega-ethane sulfonic acid.

2 amino 1 hydroxybenzene 4 sulfonamido N- ethyl-N-omega-ethane sulfonicacid.

2 amino l hydroxybenzene 4 sulfonamido N- phenyl-N-omega-ethane sulfonicacid.

2 amino 1 hydroxybenzene 4 sulfonamido N- cyclohexyl-N-omega-ethanesulfonic acid.

.EXAMPLE 2 .1 mol of the dyestuif from diazotized 4-chloro-2- amino 1hydroxybenzene and 8-acetylamino-2-hydroxynaphthalene are slurried with.1 mol of the dyestuff from diazotizedZ-ami'no-1-hydroxybenzene-4-sulfonamido-N- ethyl-N-omega-ethane sulfonicacid and 1-hydroxy-5.8-dichloronaphthalene in water, the total volumebeing 4000 volume parts. This slurry is heated to 90 C. and is broughtin solution with sodium hydroxide. The metallization and isolation arecarried out as in Example 1.

When dry, the dyestuif is a water soluble dark powder which dyes woolfrom a neutral or weakly acid bath in deep blue-black shades havingexcellent fastness properties.

EXAMPLE 3 .1 mol of the dyestufi from diazotized 4-chloro-2-am.no-1hydroxybenzene and 8-acetylamino-Z-hydroxynaphthalene are slurriedwith .1 mol of the dyestutf from diazotizedZ-amino-1hydroxybenzene-5-sulfonamido-N- cyclohexyl-N-ornega ethanesulfonic acid and 2-hydroxynaphthalene in water, the total volume being5000 volume parts. This slurry is heated to 90 C. and is brought intosolution with sodium-hydroxide. The metallization and isolation arecarried out as in Example 1.

When dry, the dyestuft is a water soluble dark powder which dyes woolfrom a neutral or a weakly acid bath in navy-blue shades havingexcellent fastness properties.

The Z-amino 1 hydroxybenzene 5 sulfonamido-N- cyclohexyl-N-omega-ethanesulfonic acid mentioned as one of the diazo components for the above dyecan be prepared as follows:

Chloroethane sodium sulfonate is heated with an excess ofcyclohexylamine to about 200 C. under pressure. The excesscyclohexylamine is removed by steam distillation and the resultingsolution of cyclohexyltaurine is condensed with benzoxazalone-6-sulfonicacid chloride (oxa-l) to the corresponding sulfonamide which uponsaponification with sodium hydroxide yields 2 -amino-l-hydroxybenzene 5sulfonamido N cyclohexyl-N- omega-ethane sulfonic acid.

EXAMPLE 4 .1 mol of the dyestufi from diazotized 4-nitro-2-amino-l-hydroxybenzene and 2-hydroxynaphthalene are slurried with .1 molof the dyestuff from diazotized 2- amino 1 hydroxybenzene 4 sulfonamidoN methyl-N-omega-ethane sulfonic acid and8-acetylamino-2-hydroxynaphthalene in water, the total volume being 3000volume parts. This slurry is heated to 90 C. and is brought in solutionwith sodium hydroxide. To this is added a solution of chromic'tartratecorresponding to 8 parts Cr O The mixture is held at 90 C. until themetallization is completed. The metallized dyestuii is isolated by theaddition of sodium chloride and partial neutralization with hydrochloricacid, followed by filtration.

When dry, the dyestuff is a water soluble dark powder which dyes woolfrom a neutral or weakly acid bath in full black shades having excellentfastness properties.

The monoazo-dyestufi' from diazotized 4-nitro-2-aminol-hydroxybenzeneand 2-hydroxynaphthalene can be replaced by the monoazo-dyestuif fromdiazotized 4-chlor- 5-nitro-2-amino-l-hydroxybenzene and 2-hydroxynaphthalene. The resulting metallized dyestufi dyes wool in bluer shadesthan the one first described in this example.

EXAMPLE 5 .1 mol of the dyestutf from diazotizedS-nitro-Z-aminol-hydroxybenzene and Z-hydroxynaphthalene are slurriedwith .1 mol of the dyestuff from diazotized 4-nitro-2-amino-l-hydroxybenzene and 2-amino-naphthalene-6-sul--fonamido-N-methyl-N-omega-ethane sulfonic acid in water, the totalvolume being 2000 volume parts. This slurry is heated to C. and broughtin solution with sodium hydroxide. To this is added a solution of 28parts cobalt sulfate (CoSO .7H O) in parts water and 136 parts ammonia26 B. The mixture is held at 90 C. until the metallization is completed.The metallized dyestufi is isolated by the addition of sodium chloride,followed by filtration. 7

When dry, the dyestuif is a water soluble dark powder, which dyes woolfrom a neutral or weakly acid bath in deepv greenisheblack shades havingexcellent fastness properties.

The 2-amino naphthalene-6-sulfonamido-Nmethyl-N- omega-ethane sulfonicacid can be obtained from 2- acetyl amino naphthalene-6-sulfonic acidchloride by treatment with a water solution of methyltaurine followed byan acid hydrolysis of the acetyl group.

The 5-nitro-2-amino-l-hydroxybenzene can be advantageously replaced withpicramic acid. The final metallized dyestufi, dyes wool in full blackshades.

EXAMPLE 6 .1 mol of the dyestutf from diazotized4-nitro-2-aminol-hydroxybenzene and 8 acetylamino 2 hydroxynaphthaleneare slurried in water with .1 mol of the dyestuff from diazotized4-nitro-2-amino-l-hydroxybenzene and 2- aminonaphthalene 5sulfonamido-N-methyl-N-omegaethane sulfonic acid, the total volume being3000 volume parts. This slurry is heated to 90 C. and brought insolution with sodium hydroxide. To this is added a solution of 28 partscobalt sulfate ('CoSO .7H O) in 100 parts water and 136 parts ammonia 26B. The mixture is held at 90 C. until the metallization is completed.The metallized dyestuif is isolated by the addition of sodium chloridefollowed by filtration.

When dry, the dyestufl is a water soluble dark powder, which dyes woolfrom a neutral or weakly acid bath in deep black shades having excellentfastness properties.

The 2 aminonaphthalene-5-sulfonamido-N-methyl-N- methyl-N-omega ethanesulfonic acid can be obtained from 2-acetylaminonaphthalene-5-sulfonicacid chloride by treatment with a water solution of methyltaurine,followed by an acid hydrolysis of the acetyl group.

What is claimed is:

1. A chromiferous azo-dyestuft composition prepared by metalizing twomolecules of different monoazo-dyestuifs with a chromium compound insuch a manner that the ratio of the. complexly bound chromium to that ofthe azo components is substantially one to two, and the ratio of the twodiiferent monoazo-dyestuffs to each other is substantially one to one,one monazo-dyestuff corresponding to the general formula:

where A and A are members of the group consisting of hydrogen, halogen,and the nitro radical and B is a member of the group consisting ofhydrogen and the acetyl amino radicalythe other monoazo dyestuficorresponding .and l the :other monoa zo-dyestuif corresponds to thewherewA and 'B are as above and R is a member of the 10 group consistingof hydrogen, methyl, ethyl y y References Cited mthe file of tlzuspatent ethyl, phenyl, and cyclohexyl radicals. UNITED STATES N 2. vAchromiferous azo-dyestufi composition prepared 2,776,956 Zickendraht etal. JanQS, 1 957 .by metallizing two molecules of different m0noaZ0-dye2,816,101 Breig et a1. Dec. 10, 1957 stuffs with a chromium compoundinsuch a manner that 5 2,824,867 Keller et a1. Feb. 25, 1958 the ratioof the complexly bound chromium to that of the 2,824,868 Keller et al.Feb. 25, 1958 :azo components is substantially two to one, and the ratioof the two different monoazo-dyestuffs to each other is substantiallyone to one, one of which corresponds to the formula: 20

OH 7 OH

1. A CHROMIFEROUS AZO-DYESTUFF COMPOSITION PREPARED BY METALIZING TWOMOLECULES OF DIFFERENT MONOAZO-DYESTUFFS WITH A CHROMIUM COMPOUND INSUCH A MANNER THAT THE RATIO OF THE COMPLEXLY BOUND CHROMIUM TO THAT OFTHE AZO COMPONENTS IS SUBSTANTIALLY ONE TO TWO, AND THE RATIO OF THE TWODIFFERENT MONOAZO-DYESTUFFS TO EACH OTHER IS SUBSTANTIALLY ONE TO ONE,ONE MONAZO-DYESTUFF CORRESPONDING TO THE GENERAL FORMULA: